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CN-116444863-B - Preparation method of barrier antibacterial TPU composite film

CN116444863BCN 116444863 BCN116444863 BCN 116444863BCN-116444863-B

Abstract

The invention discloses a preparation method of a barrier antibacterial TPU composite film, which comprises the steps of preparing graphene oxide by using an improved hummers, preparing fluorinated graphene by using hydrofluoric acid as a fluorine source, preparing fluorinated graphene quantum dots by using the fluorinated graphene as a carbon source under the conditions of an oxidant and alkalinity, dissolving chitosan in an acetic acid solution, and reacting with FGQDs under the action of dodecanol to form a barrier antibacterial agent CS/FGQDs. The TPU composite film produced by the barrier antibacterial agent not only has a certain improvement on the antibacterial property, but also improves the barrier property, and can generate huge social and economic benefits.

Inventors

  • ZHENG YUYING
  • WU QINGCHU

Assignees

  • 福州大学

Dates

Publication Date
20260508
Application Date
20230424

Claims (5)

  1. 1. A preparation method of a barrier antibacterial agent is characterized by comprising the following steps: (1) Preparing graphene oxide GO by adopting the improved hummers; (2) Dispersing the GO prepared in the step (1) in deionized water to prepare GO dispersion liquid, taking the GO dispersion liquid in a beaker, weighing hydrofluoric acid, adding the GO dispersion liquid into the beaker, stirring the mixture for 0.5h, transferring the mixture into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction to obtain FGO; (3) Dispersing FGO prepared in the step (2) in deionized water, adding hydrogen peroxide and ammonia water after ultrasonic treatment for 2 hours, carrying out reflux reaction for 6 hours at 70 ℃, carrying out suction filtration, dialyzing, and freeze-drying to obtain FGQDs; (4) Dissolving chitosan in acetic acid solution, stirring for 6 hours to fully dissolve the chitosan, adding dodecanol, stirring for 0.5 hour, adding FGQDs, stirring for 12 hours at room temperature, and drying at 60 ℃ to obtain the barrier antibacterial agent CS/FGQDs; The concentration of the GO dispersion liquid in the step (2) is 2mg/ml, the volume ratio of the GO dispersion liquid to hydrofluoric acid is 40:2, the hydrothermal condition is 150 ℃, and the reaction time is 24 hours; The dosage ratio of FGO, hydrogen peroxide and ammonia water used in the step (3) is 1mg to 1ml to 0.1ml, and the dialysis time is 3d; The concentration of the acetic acid solution used in the step (4) is 1wt%, the mass ratio of chitosan to dodecanol is 1:0.7, and the mass ratio of chitosan to FGQDs is 7:3.
  2. 2. A barrier antimicrobial agent made by the method of claim 1.
  3. 3. The use of the barrier antibacterial agent according to claim 2 for preparing TPU composite films, wherein the barrier antibacterial agent and TPU solution are mixed according to a certain proportion, and a film coating instrument is adopted for preparing the TPU composite films with barrier antibacterial performance.
  4. 4. The method of claim 3, wherein the barrier antibacterial agent is used in an amount of 1-3% by weight of the TPU composite film.
  5. 5. The use of the barrier antibacterial agent according to claim 3 for preparing TPU composite film, wherein the TPU solution is prepared by dissolving TPU particles in DMF at a certain temperature, the ratio is 1g:5ml, the reaction temperature is 80 ℃ and the reaction time is 5h, the blending is prepared by mechanically stirring CS/FGQDs and TPU solution until no bubble is generated, and the temperature of a film coating instrument is 80 ℃.

Description

Preparation method of barrier antibacterial TPU composite film Technical Field The invention belongs to the field of polymer composite materials, and particularly relates to a preparation method of a barrier antibacterial agent and application of the barrier antibacterial agent in preparation of TPU composite films. Background Thermoplastic polyurethane elastomers (TPU) are linear polymers obtained by block copolymerization of diisocyanates, small molecule polyols, large molecule polyesters or polyether polyols, which have been widely used in the fields of adhesives, coatings, composites, biomedical materials, and the like. However, with the development of science and technology, in some fields, such as the field of films, higher requirements are put on the antibacterial property and the barrier property of the TPU composite film. The water vapor and gas molecules can easily permeate through the TPU film, so that the application of the TPU film in the barrier field is affected, and due to a large amount of ester bonds and ether bonds of the TPU film and certain temperature and humidity, bacteria are easy to adhere to the surface of the TPU film and grow and reproduce to form a layer of biological film. The carbon quantum dots have the advantages of excellent optical properties, good water solubility, low toxicity, environmental friendliness, wide raw material sources, low cost, good biocompatibility and the like, and the methods can be roughly classified into a 'top-down' synthesis method and a 'bottom-up' synthesis method according to the carbon sources, wherein the latter synthesis method mainly adopts organic small molecules or oligomers as carbon sources, and citric acid, glucose, polyethylene glycol, urea, ionic liquids and the like are commonly used. The fluorinated graphene refers to a novel flaky nano carbon material formed by partially or completely fluorinating carbon atoms in the graphene. The fluorine atoms have lower polarizability, strongest electronegativity and smaller van der Waals radius, and the doping of fluorine elements, perfluorinated groups and graphene endows the graphene with unique physicochemical properties and physiological activity. The rapid development and growth of graphene families are also being actively promoted. GQDs have excellent properties and heteroatom doping GQDs can further tailor their band structure to yield unexpected properties. So far, GQDs have been rapidly developed for use in solar cells, photodetectors, imaging and light emitting diodes. Doping heteroatoms is an effective material modification method in order to further expand the application of GQDs. Through doping, the adjustable gaps in GQDs can be effectively designed, the surface structure is modified, and other old groups are added to realize chemical functionalization. The chitosan is a product of removing partial acetyl of natural polysaccharide chitin, has multiple physiological functions of biodegradability, biocompatibility, no toxicity, bacteriostasis, anticancer, lipid reduction, immunity enhancement and the like, and is widely applied to various fields of food additives, textiles, agriculture, environmental protection, beauty and health care, cosmetics, antibacterial agents and the like and other daily chemical industries. Chitosan is insoluble in water, alkali and general organic solvents, but because of the existence of-NH 2 groups in the chitosan structural units, chitosan is extremely easy to react with acids to form salts, and thus, chitosan can be dissolved in many dilute inorganic acids such as hydrochloric acid, formic acid, acetic acid, lactic acid, malic acid, ascorbic acid, etc., or some organic acids. The active adsorption center of chitosan is surface free amino, and many inorganic acid, organic acid and acid compound, even amphoteric compound, can be adsorbed and combined by chitosan. Disclosure of Invention The invention aims at overcoming the defects of the prior art and provides a preparation method and application of a barrier antibacterial agent. The TPU composite film produced by the barrier antibacterial agent not only has a certain improvement on the antibacterial property, but also improves the barrier property, and can generate huge social and economic benefits. In order to achieve the above purpose, the invention adopts the following technical scheme: A preparation method of a barrier antibacterial agent comprises the steps of preparing graphene oxide by a modified hummers method, preparing fluorinated graphene by taking hydrofluoric acid as a fluorine source, preparing FGQDs by taking fluorinated graphene as a carbon source, and performing grafting reaction on chitosan and FGQDs in an acetic acid solution under the action of dodecanol to form the barrier antibacterial agent CS/FGQDs. The preparation method of the barrier antibacterial agent comprises the following steps: (1) Preparing graphene oxide GO by adopting the improved hummers; (2) Dispersing the GO prepared